Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/71—Monoisocyanates or monoisothiocyanates
  • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/83—Chemically modified polymers
  • C08G18/837—Chemically modified polymers by silicon containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the invention relates to two-component compositions based on silane-functional polymers, suitable for use as adhesives, sealants or coatings.
• Hardenable masses based on silane-functional polymers are known. They are characterized by hardening without bubbles and high adhesive strength. Most of the known compositions of this type are formulated as single-component compositions which harden with the aid of atmospheric moisture. This has the disadvantage that the time required for complete hardening, i.e., reaching the final strength, is relatively long, since the moisture must enter the composition by diffusion, which takes place only very slowly in the case of thick-layer implementations and during the application of the composition, but especially during the bonding of substrates that are impermeable to moisture.
• compositions based on silane-functional polymers with better mechanical properties, especially higher strength and viscoelasticity, can be obtained, for example, if the silane-functional polymer is combined with an epoxy resin as a hybrid system, for example as described in EP0186191.
• the goal of the present invention therefore is to overcome the problems with the prior art and thus supply a composition based on silane-functional polymers which, independently of the application conditions such as temperature and relative humidity, hardens quickly and without leaving behind a sticky surface, and in the hardened state, has high strength and viscoelasticity, good adhesion to various substrates, and high thermal stability.
• the composition in the non-cross-linked state, should have a long shelf life and good applicability, especially at room temperature.
• composition according to the invention lies in the fact that if necessary it can be produced in such a manner that immediately after application it has good stability and slip resistance, which is desirable in many applications, for example in the application of the composition to vertical surfaces.
• composition according to the invention in contrast to known hybrid systems based on silane-functional polymers and epoxy resin, gives off little odor during application.
• the present invention relates to a two-component composition consisting of a component A comprising
• At least one hardener or accelerator for epoxy resins at least one hardener or accelerator for epoxy resins
• At least one aqueous emulsion of at least one epoxy resin is at least one aqueous emulsion of at least one epoxy resin.
• Substance names beginning with “poly,” such as polyol or polyisocyanate, in the present document designate substances which contain in their formula two or more of the functional groups occurring in their name per molecule.
• polymer in the present document covers on one hand a group of macromolecules that are chemically uniform but differ with regard to degree of polymerization, molecular weight and chain length and were produced by a polyreaction (polymerization, polyaddition, polycondensation).
• the term covers derivatives of such a group of macromolecules obtained by polyreaction, thus compounds that were obtained by reactions, such as additions or substitutions, of functional groups on pre-existing macromolecules and which may be chemically uniform or non-uniform.
• the term furthermore covers so-called prepolymers, in other words, reactive oligomeric pre-adducts, the functional groups of which participate in the make-up of macromolecules.
• polyurethane polymer covers all polymers produced by the so-called diisocyanate polyaddition method. This also includes polymers that include few or no urethane groups. Examples of polyurethane polymers are polyether-polyurethanes, polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
• silane and “organosilane” respectively indicate compounds that on one hand contain at least one, generally two or three, alkoxy groups or acyloxy groups attached via Si—O bonds directly to the silicon atom, and on the other hand at least one organic radical attached via a Si—C bond directly to the silicon atom.
• Such silanes are also known to the person skilled in the art as organoalkoxysilanes or organoacyloxysilanes.
• silane group designates the silicon-containing group attached to the organic moiety of the silane via the Si—C bond.
• the silanes, or their silane groups have the characteristic of hydrolyzing upon contact with moisture.
• organosilanols are formed, i.e., organosilicon compounds containing one or more silanol groups (SiOH groups), and, through subsequent condensation reactions, organosiloxanes, i.e., organosilicon compounds containing one or more siloxane groups (Si—O—Si-groups).
• silane-functional designates compounds containing silane groups.
• silane-functional polymers are thus polymers that contain at least one silane group.
• Aminosilanes and mercaptosilanes are the respective terms used for organosilanes in which the organic radical contains an amino group of a mercapto group.
• Primary aminosilanes is the term used for aminosilanes that contain a primary amino group, thus an NH 2 group bound to an organic radical.
• secondary aminosilanes are aminosilanes that contain a secondary amino group, thus an NH group that is bound to two organic radicals.
• molecular weight is defined in the present document as the average molecular weight M n (number-average).
• room temperature designates a temperature of 23° C.
• Component A of the composition according to the invention contains at least one silane-functional polymer P, which especially contains end groups of formula (I).
• radical R 3 represents a linear or branched, monovalent carbohydrate radical with 1 to 8 C atoms, especially a methyl or ethyl group.
• the radical R 4 represents a linear or branched, divalent hydrocarbon radical with 1 to 12 C atoms, which optionally contains cyclic and/or aromatic fractions, and optionally one or more hetero atoms, especially one or more nitrogen atoms.
• R 4 represents a linear or branched alkylene group with 1 to 6 C atoms, preferably methylene or 1,3-propylene, particularly preferably 1,3-propylene.
• the radical R 5 represents an acyl radical or a linear or branched, monovalent hydrocarbon radical with 1 to 5 C atoms, especially a methyl, ethyl or isopropyl group.
• the subscript a represents a value of 0 or 1 or 2, especially a value of 0.
• R 3 and R 5 each independently represent the radicals described.
• the silane-functional polymer P is a silane-functional polyurethane polymer P1, obtainable by reacting a silane having at least one group reactive with isocyanate groups, with a polyurethane polymer having isocyanate group. This reaction is preferably performed at a stoichiometric ratio of the groups reactive toward isocyanate groups to isocyanate groups of 1:1 or with a slight excess of groups reactive toward isocyanate groups, so that the resulting silane-functional polyurethane polymer P1 is completely free from isocyanate groups.
• the silane which has at least one group reactive toward isocyanate groups with a polyurethane polymer that contains isocyanate groups
• the silane can theoretically, although not preferentially, be used in substoichiometric quantities, so that a silane-functional polymer containing both silane groups and isocyanate groups is obtained.
• the silane containing at least one group reactive toward isocyanate groups is particularly a mercaptosilane or an aminosilane, preferably an aminosilane.
• the aminosilane is preferably an aminosilane AS of formula (II),
• R 7 represents a hydrogen atom or a linear or branched, monovalent hydrocarbon radical with 1 to 20 C atoms, optionally containing cyclic moieties, or a radical of formula (III).
• radicals R 8 and R 9 each independently represent a hydrogen atom or a radical from the group consisting of —R 11 , —COOR 11 and —CN.
• the radical R 10 represents a hydrogen atom or a radical from the group consisting of —CH 2 —COOR 11 , —COOR 11 , —CONHR 11 , —CON(R 11 ) 2 , —CN, —NO 2 , —PO(OR 11 ) 2 , —SO 2 R 11 and —SO 2 OR 11 .
• the radical R 11 represents a hydrocarbon radical with 1 to 20 C atoms, optionally containing at least one hetero atom.
• suitable aminosilanes AS are primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes such as N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl-trimethoxysilane; the products from the Michael-like addition of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, (meth)acrylic acid esters, (meth)acrylic acid amides, maleic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, for example N-(3-trimethoxysilyl-propyl)-amino-succinic acid dimethyl- and -diethyl esters; and analogs
• aminosilanes AS are secondary aminosilanes, especially aminosilanes AS, in which R 7 in formula (II) is different from H.
• the Michael-like adducts are preferred, especially N-(3-trimethoxysilyl-propyl)-amino-succinic acid diethyl ester.
• ichael acceptor designates compounds which, as a result of the electron-accepting radical activated double bonds that they contain, can undergo nucleophilic addition reactions with primary amino groups in a manner analogous to Michael addition (Hetero-Michael-Addition).
• Suitable isocyanate group-containing polyurethane polymers for producing a silane-functional polyurethane polymer P1 are, for example, polymers that can be obtained by reacting at least one polyol with at least one polyisocyanate, especially a diisocyanate. This reaction can be performed by reacting the polyol and the polyisocyanate using the usual methods, for example at temperatures of 50° C. to 100° C., optionally also using suitable catalysts, wherein the polyisocyanate is added in such a way that the isocyanate groups thereof are present in a stoichiometric excess relative to the hydroxyl groups of the polyol.
• the excess of polyisocyanate is selected such that after all of the hydroxyl groups of the polyol have reacted, a free isocyanate group content of 0.1 to 5% by weight, preferably 0.1 to 2.5% by weight, particularly preferably 0.2 to 1% by weight, based on the total polymer, will remain in the resulting polyurethane polymer.
• the polyurethane polymer can be produced with the aid of plasticizers, wherein the plasticizers used do not contain any groups reactive toward isocyanates.
• Preferred polyurethane polymers are those with the free isocyanate group mentioned, obtained from the reaction of diisocyanates with high-molecular-weight diols in an NCO:OH ratio of 1.5:1 to 2.2:1.
• Especially suitable polyols for producing the polyurethane polymers are polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
• polyether polyols also called polyoxyalkylene polyols or oligoetherols are those that are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule with two or more active hydrogen atoms, for example water, ammonia or compounds with several OH or NH groups, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols,
• Both polyoxyalkylene polyols which have a low degree of unsaturation (measured according to ASTM D-2849-69 and stated in milliequivalents of unsaturation per g polyol (mEq/g)), produced for example with the aid of so-called Double Metal Cyanide complex catalysts (DMC-catalysts), and polyoxyalkylene polyols with a higher degree of unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates may be used.
• DMC-catalysts Double Metal Cyanide complex catalysts
• anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates
• polyoxyethylene polyols and poly oxy propylene polyols especially polyoxyethylene diols, poly oxy propylene diols, polyoxyethylene triols and poly oxy propylene triols.
• polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation of less than 0.02 mEq/g and with a molecular weight in the range of 1000 to 30,000 g/mol, as well as polyoxyethylene diols, polyoxyethylene triols, poly oxy propylene diols and poly oxy propylene triols with a molecular weight of 400 to 20,000 g/mol.
• ethylene oxide-endcapped (“EO-endcapped”) poly oxy propylene polyols are also particularly suitable.
• EO-endcapped ethylene oxide-endcapped
• poly oxy propylene-polyoxyethylene polyols obtained for example in that pure poly oxy propylene polyols, especially poly oxy propylene diols and -triols, are further alkoxylated with ethylene oxide after completion of the polypropoxylation reaction and thus contain primary hydroxyl groups.
• polyoxypropylene-polyoxyethylene diols and polyoxypropylene-polyoxyethylene triols are preferred.
• hydroxyl group-endcapped polybutadiene polyol for example those produced by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene and the hydrogenation products thereof.
• styrene-acrylonitrile grafted polyether polyols for example those commercially available under the trade name of Lupranol® from the firm of Elastogran GmbH, Germany.
• polyester polyols are polyesters containing at least two hydroxyl groups and produced by known methods, especially polycondensation of hydroxycarboxylic acids or polycondensation of aliphatic and/or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
• polyester polyols produced from dihydric to trihydric alcohols, such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or anhydrides or esters thereof, for example succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic acid anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid
• polyester diols especially those produced from adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acids or from lactones such as ⁇ -caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimer fatty acid diol and 1,4-cyclohexanedimethanol as divalent alcohol.
• polycarbonate polyols are those obtained by reacting, for example, the above-mentioned alcohols used for making up the polyester polyols, alcohols with dialkyl carbonates such as dimethyl carbonate, diary carbonates such as diphenyl carbonate or phosgene.
• dialkyl carbonates such as dimethyl carbonate
• diary carbonates such as diphenyl carbonate or phosgene.
• polycarbonate diols especially amorphous polycarbonate diols.
• Additional suitable polyols are poly(meth)acrylate polyols.
• polyhydroxy-functional fats and oils for example natural fats and oils, especially castor oil, or polyols obtained by chemical modification of natural fats and oils, so-called oleochemical polyols, which are obtained for example by epoxidation of unsaturated oils and subsequent ring opening with carbonic acids or alcohols, epoxy-polyesters or epoxy-polyethers, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils.
• polyols obtained from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by ester exchange or dimerization, of the degradation products or derivatives obtained in this way.
• Suitable degradation products of natural fats and oils are especially fatty acids and fatty alcohols as well as fatty acid esters, especially the methyl esters (FAME), which can be derivatized for example by hydroformylation and hydrogenation to hydroxy-fatty acid esters.
• FAME methyl esters
• polyhydrocarbon polyols also known as oligohydrocarbonols, for example polyhydroxyfunctional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those manufactured by the firm of Kraton Polymers, USA, or polyhydroxyfunctional copolymers from dienes such as 1,3-butanedienes or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxyfunctional polybutadiene polyols, for example those that can be obtained by copolymerization of 1,3-butadiene and allyl alcohol and may also be hydrogenated.
• polyhydrocarbon polyols also known as oligohydrocarbonols
• polyhydroxyfunctional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers such as those manufactured by the firm of Kraton Polymers, USA
• polyhydroxyfunctional copolymers from dienes such as 1,3
• polyhydroxyfunctional acrylonitrile/butadiene copolymers which can be produced for example from epoxides or amino alcohols and carboxyl-endcapped acrylonitrile/butadiene copolymers, and which are commercially available under the name of Hypro® CTBN from the firm of Emerald Performance Materials, LLC, USA.
• These polyols mentioned preferably have a mean molecular weight of 250 to 30,000 g/mol, especially of 1000 to 30,000 g/mol, and a mean OH functionality in the range of 1.6 to 3.
• polyester polyols and polyether polyols especially polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene-polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene-polyoxyethylene diol and polyoxypropylene-polyoxyethylene triol.
• small amounts of low-molecular-weight divalent or polyvalent alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimer fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylit
• monovalent alcohols may additionally be used, for example butanol, 2-ethylhexanol or an alcohol-initiated polyoxyalkylene mono-ol.
• polyisocyanates used for producing the polyurethane polymers may include commercial polyisocyanates, especially diisocyanates.
• suitable diisocyanates are 1,6-Hexamethylene diisocyanate (HDI), 2-methyl-pentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-Dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4′-diphenylmethane diisocyanate and perhydro-4,4′-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3
• Particularly suitable polyisocyanates are HDI, TMDI, IPDI, TDI and MDI, especially IPDI.
• silane-functional polymers P1 are commercially under the trade names of Polymer ST, for example Polymer ST50, from the firm of Hanse Chemie AG, Germany, and under the trade name of Desmoseal® from the firm of Bayer MaterialScience AG, Germany.
• the silane-functional polymer P is a silane-functional polyurethane polymer P2, obtainable by reacting an isocyanatosilane IS with a polymer that has end groups reactively functional with respect to isocyanate groups. This reaction takes place at stoichiometric proportions of the isocyanate groups to the reactive functional end groups relative to isocyanate groups of 1:1 or with a slight excess of the reactive functional end groups, for example at temperatures of 20° C. to 100° C., optionally using catalysts.
• Suitable as the isocyanatosilane IS are compounds of formula (V).
• isocyanatosilanes IS of formula (V) are isocyanatomethyl trimethoxysilane, isocyanatomethyl dimethoxy methylsilane[,] 3-Isocyanatopropyltrimethoxysilane[,] 3-Isocyanatopropyldimethoxymethylsilane and the analogues thereof with ethoxy or isopropoxy groups in place of the methoxy groups on the silicon.
• the polymer preferably contains hydroxyl groups as reactive functional end groups toward isocyanate groups.
• Suitable hydroxyl group-containing polymers are on one hand the previously mentioned polyols, especially high-molecular-weight polyoxyalkylene polyols, preferably polyoxypropylene diols with a degree of unsaturation of less than 0.02 mEq/g and with a molecular weight in the range of 2000 to 30,000 g/mol, especially those with a molecular weight in the range of 4000 to 30,000 g/mol.
• hydroxyl group-containing, especially hydroxyl group-endcapped, polyurethane polymers are also suitable for reacting with isocyanatosilanes IS of formula (V).
• Such polyurethane polymers are obtainable by reacting at least one polyisocyanate with at least one polyol. This reaction can be performed in that the polyol and the polyisocyanate are made to react by customary methods, for example at temperatures of 50° C. to 100° C., optionally using suitable catalysts, wherein the polyol is added in such a manner that its hydroxyl groups are present in stoichiometric excess in relation to the isocyanate groups of the polyisocyanate.
• a ratio of hydroxyl groups to isocyanate groups of 1.3:1 to 4:1, especially of 1.8:1 to 3:1 is preferred.
• the polyurethane polymer can be manufactured using plasticizers, wherein the plasticizers used do not contain any groups reactive toward isocyanates.
• polys and polyisocyanates are suitable for this reaction as were already mentioned as suitable for producing an isocyanate group-containing polyurethane polymer that is used for producing a silane-functional polyurethane polymer P1.
• silane-functional polymers P2 are those that are commercially available under the trade names of SPUR+® 1010LM, 1015LM and 1050MM from the firm of Momentive Performance Materials Inc., USA, and under the trade names of Geniosil® STP-E15, STP-10 and STP-E35 from the firm of Firma Wacker Chemie AG, Germany.
• the silane-functional polymer P is a silane-functional polymer P3 which is obtainable by a hydrosilylation reaction of polymers with terminal double bonds, for example poly(meth)acrylate polymers or polyether polymers, especially of allyl-endcapped polyoxyalkylene polymers, described for example in U.S. Pat. No. 3,971,751 and U.S. Pat. No. 6,207,766, the total disclosure of which is herewith incorporated.
• silane-functional polymers P3 are commercially available under the trade names MS PolymerTM S203H, S303H, S227, S810, MA903 and S943, SilylTM SAX220, SAX350, SAX400 and SAX725, SilylTM SAT350 and SAT400, as well as XMAPTM SA100S and SA310S from the firm of Kaneka Corp., Japan, and under the trade names Excestar® S2410, S2420, S3430, S3630, W2450 and MSX931 from the firm of Asahi Glass Co, Ltd., Japan.
• silane-functional polymers P are silane-functional polymers P1 and silane-functional polyurethane polymers P3. Particularly preferred are silane-functional polymers P1.
• the silane-functional polymer P is usually present in a quantity of 10 to 80% by weight, especially in a quantity of 15 to 70% by weight, preferably 20 to 60% by weight, based on the total composition.
• Component A of the composition according to the invention also contains, in addition to the silane-functional polymer, at least one hardener or accelerator for epoxy resins.
• these are especially polyamines, for example isophorone diamine, m-xylylenediamine, polyether amines such as those that are commercially available under the trade names Jeffamine® from Huntsman International LLC, USA, polyethylenimines, polyamidoamines, polyalkyleneamines such as diethylenetriamine (DE-TA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) or pentaethylenhexamine (PEHA), amine-epoxy adducts, pentamethyl diethylenetriamine, N,N-dimethyl-N′-(dimethylaminopropyl)-1,3-propanediamine, bis(2-dimethylaminoethyl)ether, bis-(dimethylaminoethyl)-piperazine, N,
• accelerators especially phosphites, [or] acids, especially phosphoric acid and carboxylic acids, may be used.
• Preferred hardeners or accelerators for epoxy resins are tertiary polyamines, especially pentamethyl-diethylene triamine, N,N-dimethyl-N′-(dimethylaminopropyl)-1,3-propanediamine,bis(2-dimethylaminoethyl)ether, bis-(dimethylaminoethyl)-piperazine, N,N′-dimethylpiperazine; Mannich bases, especially dimethylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol and 2,4,6-tris((3-(dimethylamino)propyl)aminomethyl)phenol; as well as imidazoles, especially 1-methylimidazole, 1-ethylimidazole, 1-vinylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-heptadecylimidazole, 2-ethyl-4-
• the fraction of the hardener or accelerator for epoxy resins is preferably 0.5 to 15% by weight, especially 1 to 10% by weight, based on component A.
• Component B of the composition according to the invention comprises at least one aqueous emulsion of at least one epoxy resin.
• the epoxy resin is preferably a liquid resin.
• Preferred liquid epoxy resins have the formula (VI).
• substituents R 1 and R 2 independently represent either H or CH 3 .
• subscript r represents a value of 0 to 1.
• r represents a value of ⁇ 0.2.
• DGEBA diglycidyl ethers of bisphenol A
• A/F refers to a mixture of acetone with formaldehyde, which is used as an educt in the production of bisphenol A/F.
• Suitable liquid resins are commercially available under the trade names Araldite® GY 250, Araldite® GY 282, Araldite® PY 304 from Huntsman International LLC, USA, or D.E.R.® 330 or D.E.R.® 331 from Dow Chemical Company, USA, or under the trade names Epikote® 828 or Epikote® 862 from Hexion Specialty Chemicals Inc., USA.
• the epoxy resin is typically present in unmodified form. In particular, it is not modified for better emulsifiability, for example with a fatty acid.
• the aqueous emulsion of at least one epoxy resin optionally contains at least one reactive diluent.
• Suitable reactive diluents include especially monofunctional epoxides, preferably glycidylated fatty alcohols.
• the emulsion also contains at least one external emulsifier, especially a nonionic emulsifier, for example a fatty alcohol ethoxylate.
• a nonionic emulsifier for example a fatty alcohol ethoxylate.
• the emulsion preferably has an emulsifier content of ⁇ 10% by weight, especially ⁇ 5% by weight.
• the emulsion advantageously has a solids content of 60 to 90% by weight, especially of 70 to 90% by weight, preferably of 75 to 85%.
• the aqueous emulsion of at least one epoxy resin contains about 10 to 40% by weight, especially 10 to 30% by weight, preferably 15 to 25% by weight, of water.
• the mean particle size (droplet diameter) of the emulsion especially falls in the range of 0.05 of 10 ⁇ m, especially von 0.1 to 7 ⁇ m, particularly preferably of 0.2 to 5 ⁇ m.
• the emulsion preferably has a narrow particle size distribution, wherein the size ratio of the largest to the smallest particle has a value in the range of preferably ⁇ 20.
• the particle size distribution is such that 90% of the particles in the emulsion are smaller than 6 ⁇ m, preferably smaller than 4 ⁇ m, particularly preferably smaller than 3 ⁇ m.
• the emulsion has a low tendency toward creaming or hardening and thus has a long storage life.
• the preparation of the emulsion preferably takes place in a continuous process, especially using a stator-rotor mixer.
• a stator-rotor mixer Such a method is known to the person skilled in the art.
• the particular advantages of such a method lie in the fact that the emulsion can be produced without the addition of solvents even if the viscosity of the epoxy resin is relatively high.
• the manufacturing preferably takes place without addition of solvents.
• components A and B contain additional components such as fillers and reinforcing agents, plasticizers or diluents, hardeners and crosslinking agents, accelerators and catalysts, stabilizers, adhesive promoters, rheology promoters, drying agents and the like.
• additional components such as fillers and reinforcing agents, plasticizers or diluents, hardeners and crosslinking agents, accelerators and catalysts, stabilizers, adhesive promoters, rheology promoters, drying agents and the like.
• Component A of the composition according to the invention especially contains at least one catalyst for crosslinking the silane-functional polymers by means of moisture.
• catalysts are especially organotin compounds, for example dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetylacetonate and dioctyltin diacetylacetonate; titanates and zirconates, for example tetraisobutoxytitanate and diisobutoxytitanium-bis-(ethyl acetoacetate); nitrogen compounds, especially tertiary amines, for example N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine and 1,4-diazabicyclo[2.2.2]octane, and amidines and guanidines, for example 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,1,3,3-tetramethylgu
• Component A of the composition according to the invention further contains especially at least one aminosilane, an epoxysilane or a mercaptosilane.
• Particularly suitable are 3-aminopropyl-dialkoxyalkylsilanes, 3-aminopropyl-trialkoxysilanes, N-(2-aminoethyl)-3-aminopropyl-dialkoxyalkylsilanes, N-(2-aminoethyl)-3-aminopropyl-trialkoxysilanes, 3-glycidoxypropyltrialkoxysilanes and 3-mercaptopropyl-trialkoxysilanes.
• the use of such an aminosilane in component A of the composition according to the invention can result in improved compatibility of the different phases and covalent binding of the silane-functional polymer with the epoxy resin after mixing the components.
• component A of the composition according to the invention additionally contains at least one filler.
• the filler influences both the rheologic properties of the not fully hardened composition and the mechanical properties and surface texture of the fully hardened composition.
• Suitable fillers are inorganic and organic fillers, for example natural, ground or precipitated calcium carbonates, optionally coated with fatty acids, especially stearic acid, barium sulfate, calcined kaolins, aluminum oxide, aluminum hydroxide, silica, especially highly dispersed silica from pyrolysis processes, carbon black, especially industrially manufactured carbon black, PVC powder or hollow beads.
• Preferred fillers are calcium carbonate, calcined kaolins, carbon black, highly dispersed silica and flame retardant fillers, such as hydroxy-ides or hydrates, especially hydroxides or hydrates of aluminum, preferably aluminum hydroxide.
• a suitable quantity of filler in component A for example falls in the range of 20 to 70% by weight, preferably 30 to 60% by weight, based on the total composition.
• component A of the composition according to the invention may contain additional components, for example plasticizers such as esters of organic carboxylic acids or anhydrides thereof, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacates, polyols, for example polyoxyalkylene polyols or polyester polyols, organic phosphoric and sulfonic acid esters or polybutene; solvents; fibers, for example made of polyethylene; dyes; pigments; rheology modifiers such as thickeners or thixotropic agents, for example urea compounds of the type described as “thixotropy endowing agent” in WO 02/48228 A2 on pages 9 to 11, polyamide waxes, bentonites or pyrogenic silicas; adhesion promoters, for example epoxysilanes, (meth)acryl
• compositions may also be used such as single-component, moisture-hardening compositions based on silane-functional polymers, especially as adhesives, sealants or coatings, and commercially available for example under the trade names Sikaflex® or SikaBond® from Sika Buch AG.
• Component B also optionally contains, in addition to the aqueous emulsion of at least one epoxy resin, a silane selected from the group consisting of epoxysilanes, especially 3-glycidoxypropyl-dimethoxymethyl silane, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyl-triethoxysilane, (meth)acrylsilane, especially 3-methacryloxypropyl-trimethoxysilane, and anhydridosilane, especially (trimethoxysi-lyl)propyl-succinic acid anhydride or 3-(triethoxysilyl)propyl succinic acid anhydride.
• a silane selected from the group consisting of epoxysilanes, especially 3-glycidoxypropyl-dimethoxymethyl silane, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyl-triethoxysilane, (meth)acrylsilane,
• the silane in component B is preferably an epoxysilane or a (meth)acrylsilane.
• silane in component B of the composition according to the invention can produce improved compatibility of the different phases and covalent bonding of the silane-functional polymers with the epoxy resin after mixing the components.
• component B optionally contains especially a rheology aid or a filler.
• Component A of the previously described two-component composition is manufactured and stored in the absence of moisture.
• component A is storage-stable, i.e., as long as moisture is excluded it can be stored in a suitable package or arrangement over a period of several months up to a year or longer without undergoing a change in its application properties or its properties after hardening to any extent relevant for use.
• Component B is typically also stable when stored under normal atmospheric conditions.
• the two components A and B are preferably stored at room temperature in a drum that is impermeable to air, wherein the drum for component A especially consists of plastic (polyolefin) or of metal (aluminum) with an interior coating.
• components A and B are mixed together, for example by stirring, kneading, rolling or the like, but especially using a static mixer or with the aid of a dynamic mixer.
• component A comes into contact with the water in the aqueous emulsion of at least one epoxy resin from component B, which leads to cross-linking of the silane-functional polymers in the composition.
• component B is preferably used in a proportion relative to component A such that at least 50%, preferably 100%, of all silane groups in the total two-component composition can react with the water present in component B.
• the two-component composition according to the invention is used in such a way that the weight ratio of component A to component B is ⁇ 1:1, especially 1:1 to 100:1, preferably 1.5:1 to 50:1, particularly preferably 2:1 to 20:1.
• the complete hardening of the two-component composition especially takes place at room temperature. In certain cases it may be advantageous to harden the partially hardened composition additionally or completely with the aid of elevated temperature, for example in the range of 40 to 100° C.
• the hardening of the composition is performed in that on one hand an adequate pot life or open time is guaranteed, and on the other hand within a period of several minutes to several hours, the hardening has progressed to the point where the composition can be further processed or a bond made with the composition is self-supporting and can be transported.
• the present invention comprises the use of a previously described two-component composition as an adhesive, sealant or coating.
• the two-component composition according to the invention is especially suitable for adhering, sealing or coating of substrates made of concrete, mortar brick, tile, ceramic, plaster, natural stone such as granite or marble, glass, glass-ceramic, metal or metal alloys such as aluminum, steel, nonferrous metal, galvanized metal, wood, plastic such as PVC, polycarbonates, polymethyl(meth)acrylate, polyesters, epoxy resin, composite materials, paint or lacquer.
• substrates made of concrete, mortar brick, tile, ceramic, plaster, natural stone such as granite or marble, glass, glass-ceramic, metal or metal alloys such as aluminum, steel, nonferrous metal, galvanized metal, wood, plastic such as PVC, polycarbonates, polymethyl(meth)acrylate, polyesters, epoxy resin, composite materials, paint or lacquer.
• the two-component composition is preferably used for elastic to semi-structural adhesion and sealing applications in the construction and finishing industry as well as in vehicle construction, for example for joint sealing, roof sealing, floor bonding, façade element bonding, bonding of mounted parts, seam lining, hermetic sealing of cavities, mounting, trim bonding, windshield bonding, and composite bonding.
• the two-component composition is also especially advantageous if isocyanate-free products are to be used for reasons of occupational and health protection.
• the invention relates to a hardened composition such as is obtainable from a previously described two-component composition by mixing component A with component B.
• the invention relates to an article that has an at least partially hardened composition according to the preceding description, wherein this article especially involves an article of construction, an industrial article or a means of transport or a part thereof.
• An exemplary list of such articles includes houses, glass facades, windows, bathtubs, bathrooms, kitchens, roofs, bridges, tunnels, roads, automobiles, trucks, rail vehicles, buses, ships, mirrors, windshields, tanks, white goods, household apparatus, dishwashers, washing machines, stoves, headlights, fog lights or solar panels such as photovoltaic or solar thermal modules.
• the viscosity was measured on a thermostatically controlled ball-plate viscometer, Physica UM (ball diameter 20 mm, ball angle 1°, ball tip-plate distance 0.05 mm, shear speed 10 to 1000 s ⁇ 1 ).
• the mean particle size was measured by laser diffraction on a Sympatec device with the HELOS laser diffraction sensor.
• the odor was evaluated qualitatively by smelling the mixed composition with the nose, grading an unpleasant, penetrating amine odor as “strong” and a weak or undetectable odor as “mild.”
• the composition was applied to an upright piece of cardboard using a wooden spatula, and the flow behavior was observed.
• the creep resistance was graded “good” if the composition had drifted slightly downward within one minute without flowing down and as “very good” if it did not move at all.
• tack-free time skin formation time
• a small piece of the composition at room temperature was applied to a piece of cardboard in a layer thickness of about 3 mm and under standard climate conditions (23 ⁇ 1° C., 50 ⁇ 5% relative humidity) the time required until gently touching the surface of the composition with a LDPE pipette first failed to leave any residue on the pipette.
• the tensile strength, the elongation at break and the modulus of elasticity were determined according to DIN EN 53504 (pulling speed: 200 mm/min) on dumbbells with a length of 75 mm, at a bar length of 30 mm and a bar width of 4 mm, produced by punching out from film with a thickness of about 3 mm of the composition hardened under the respectively reported conditions.
• the Shore A hardness was determined according to DIN 53505 on test pieces hardened in a standard climate.
• Emulsion E1 68.5 parts by weight bisphenol A liquid resin (Araldite® GY-250 von Huntsman) were mixed at 50° C. with 10 parts by weight reactive diluent (Araldite® DY-E from Huntsman) and 1.5 parts by weight emulsifier (Disponil® 23 from Cognis) and then continuously emulsified with 20 parts by weight of water over a stator-rotor mixer at a rotation speed of 22 m/s. The white emulsion obtained had a creamy consistency, a viscosity at 20° C.
• Emulsion E2 68.5 parts by weight bisphenol A liquid resin (Araldite® GY-250 from Huntsman) and 10 parts by weight bisphenol F liquid resin (D.E.R.TM 354 from Dow Chemical) were mixed at 50° C. with 1.5 parts by weight emulsifier (Disponil® 23 from Cognis) and then emulsified continuously with 20 parts by weight water on a stator-rotor mixer at a rotation speed of 22 m/s.
• the white emulsion obtained was of a creamy consistency, had a viscosity at 20° C.
• compositions obtained in this way were tested for odor, stability, tack-free time and mechanical properties.
• the compositions thus obtained were tested for odor, tack-free time and mechanical properties.
• the stability of the hardened composition was investigated under thermal and hydrolytic stress in that some of the dumbbells produced as described above were additionally held for one week in a kiln at 100° C. or at 70° C. and 100% relative humidity (cataplasm conditions) and then tested for tensile strength, elongation at break and modulus of elasticity.
• Example Ref2 14 15 16 17 18 19 component A: MS polymer TM S 92 92 92 92 92 203 H Ancamine ® K54 6 6 6 6 1 1 6 IPDA — — — — — 5 5 — Catalyst 3 3 3 3 3 3 3 Aminosilane 1 1 1 1 1 1 1 1 component B: Emulsion E1 — 10 20 30 30 50 60
• compositions thus obtained were tested for tack-free time and mechanical properties after hardening.
• Example Ref2 14 15 16 17 18 19 Curing speed: Tack-free time a >8 h 8 h 4-8 h 4-8 h 4 h 4 h 8 h Mechanical properties (11 days standard climate): Tensile strength (MPa) 0.2 0.8 1.5 1.6 1.8 1.9 1.8 Elongation at break (%) 190 360 370 390 450 470 570 Modulus of elasticity 0.13 0.19 0.22 0.20 0.19 0.26 0.12 (MPa) b Mechanical properties (11 days standard climate + 2 days 80° C.): Tensile strength (MPa) 0.3 0.4 1.7 3.5 2.2 1.8 2.8 Elongation at break (%) 200 350 390 590 480 530 690 Modulus of elasticity 0.17 0.21 0.21 0.23 0.35 0.40 0.45 (MPa) b a Tack-free time. b at 0.5 to 50% elongation.
• compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.
• a hardener or accelerator for epoxy resins in the form of a tertiary amine Jeffcat® Z-
• compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.
• Example 23 24 25 26 27 28 Stability very very very very very very very very good good good good good good good good Tack-free time a (min.) 8 14 13 8 7 25 Tensile strength (MPa) 3.8 3.8 3.8 3.6 3.5 3.9 Elongation at break (%) 120 240 180 290 280 230 Modulus of elasticity b 8.7 7.3 6.2 6.2 5.5 7.8 (MPa) Shore A 70 56 70 56 52 60 a Tack-free time. b at 0.5 to 5% elongation.
• Example Ref7 29 component A Körapop 225 Comp. A 100 87.4 Ancamine® K54 — 3.3 DBU — 0.2 component B: emulsion E2 — 9.1
• compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.
• Example Ref7 29 Stability good very good Tack-free time a (min.) 27 23

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